CN112794506B - A kind of ozone catalytic oxidation device and method for processing coal chemical concentrate - Google Patents

Abstract

The invention relates to the technical field of wastewater treatment, and provides an ozone catalytic oxidation device and a method for treating coal chemical concentrate. The device provided by the present invention includes a reactor, an ozone generator, a water collecting tank and an exhaust gas processor. In the present invention, the main stirrer and the auxiliary stirrer are arranged in the reaction chamber of the reactor, which can realize the full contact between the waste water and the ozone, and the auxiliary stirrer can also destroy the ozone bubbles and increase the utilization rate of ozone; A detachable packing plate is arranged on the stirring blade of the reactor, which can realize the convenient recovery of the catalyst and the replacement of the catalyst type; the invention also sets an exhaust port on the side wall of the reaction chamber, and the exhaust port is communicated with the water collection tank, and the excess ozone enters the collection tank. Reuse in the water tank can further improve the utilization rate of ozone. The method for catalyzing the coal chemical concentrate provided by the invention has high ozone utilization rate, saves the cost of catalyst use, and can improve the removal efficiency of pollutants, and has good treatment effect.

Description

A kind of ozone catalytic oxidation device and method for processing coal chemical concentrate

technical field

The invention relates to the technical field of wastewater treatment, in particular to an ozone catalytic oxidation device and a method for treating coal chemical concentrate.

Background technique

Coal chemical concentrates contain indole, pyridine and other organic pollutants that are difficult to degrade, and common biochemical treatment methods have failed to meet the treatment requirements for coal chemical concentrates. The ozone catalytic oxidation technology generates hydroxyl radicals with stronger oxidizing ability under the action of the catalyst, and then completely oxidizes the refractory organic matter.

However, the existing ozone catalytic oxidation technology has problems such as low ozone utilization rate, insufficient contact between catalyst and wastewater, and difficulty in catalyst recovery, resulting in low wastewater treatment efficiency and serious waste of ozone and catalyst, which not only affects the wastewater treatment effect, but also Increased wastewater treatment costs.

SUMMARY OF THE INVENTION

In view of this, the present invention provides an ozone catalytic oxidation device and a method for processing coal chemical concentrate. The device provided by the invention has high ozone utilization rate, less catalyst usage, sufficient contact between ozone and catalyst, easy recovery of catalyst, and good wastewater treatment effect.

In order to achieve the above-mentioned purpose of the invention, the present invention provides the following technical solutions:

An ozone catalytic oxidation device, comprising a reactor, an ozone generator, a water collecting tank and an exhaust gas processor;

The reactor includes a reactor main body and a detachable reactor cover; the inside of the reactor main body includes an ozone gas storage layer and a reaction chamber from bottom to top; a number of microporous aerators are arranged at the bottom of the reaction chamber, the microporous aerator communicates with the ozone gas storage layer;

The reaction chamber is also provided with a main stirrer and an auxiliary stirrer, the main stirrer includes a main shaft and several stirring blades arranged on the main shaft, and the top of the main shaft is fixed on the reactor cover; Two clamping slots are arranged on the stirring blade, and a detachable packing plate is arranged in the clamping slot; one end of the stirring blade is fixed on the main shaft, and several stirring blades are installed on the main shaft in a 90° staggered manner from top to bottom;

The auxiliary stirrer is a spiral stirrer, comprising a main shaft and two stirring blades connected to the main shaft, and the main shaft is fixed at the bottom of the reaction chamber;

An exhaust port is provided on the reactor cover, and a water inlet and a water outlet are provided on the side wall of the reaction chamber;

The gas outlet of the ozone generator is communicated with the ozone gas storage layer of the reactor through an ozone pipeline, and an ozone concentration detector is arranged on the ozone pipeline;

The air inlet of the water collection tank is communicated with the exhaust port of the reactor; the water outlet of the water collection tank is communicated with the water inlet of the reactor;

The exhaust gas processor is communicated with the exhaust port of the water collecting tank.

Preferably, the number of stirring blades in the main stirrer is 2 to 6; the packing plate is provided with several holes.

Preferably, the number of the microporous aerators is 8-16, and the microporous aerators are evenly arranged at the bottom of the reaction chamber.

Preferably, the length of the main shaft of the main stirrer is 1/2 to 3/4 of the height of the reaction chamber; the length of the main shaft of the auxiliary stirrer is 1/5 to 1/4 of the height of the reaction chamber.

Preferably, the stirring blade of the main stirrer is in the shape of a cuboid, the length of the stirring blade is 3/4 to 4/5 of the lateral dimension of the reaction chamber, and the width is 1/6 to 1/5 of the height of the main stirrer. 5.

The present invention also provides a method for utilizing the device described in the above scheme to process the concentrated liquid of coal chemical industry, comprising the following steps:

(1) Pass the coal chemical concentrate into the reaction chamber, install a packing plate without catalyst in the stirring blade of the main stirrer, and carry out ozone pre-oxidation treatment under the stirring conditions of the main stirrer and the auxiliary stirrer;

(2) replace the packing plate in the stirring blade of the main agitator with the packing plate filled with activated iron particles, and carry out the first-stage catalytic ozone oxidation treatment under the stirring conditions of the main agitator and the auxiliary agitator;

(3) replacing the packing plate in the stirring blade of the main agitator with a packing plate filled with a carbon-based ozone oxidation catalyst, and carrying out the second-stage catalytic ozone oxidation treatment under the stirring conditions of the main agitator and the auxiliary agitator;

In the treatment process of the steps (1) to (3), ozone is introduced into the reaction chamber by using an ozone generator.

Preferably, in the steps (1) to (3), the stirring speed of the main agitator is 15-25 r/min, and the stirring speed of the auxiliary agitator is 100-150 r/min.

Preferably, the ozone pre-oxidation treatment time is 10-20 min, the first-stage catalytic ozone oxidation treatment time is 30-40 min, and the second-stage catalytic ozone oxidation treatment time is 30-40 min.

Preferably, the introduction rate of the ozone is 0.7-1 g/min.

Preferably, the carbon-based ozone oxidation catalyst comprises a carrier and an active component supported on the carrier, the carrier is activated carbon, and the active component is manganese dioxide; the mass of the carbon-based ozone oxidation catalyst is 100%. , the loading amount of manganese dioxide in the carbon-based ozone oxidation catalyst is 3-5%.

The invention provides an ozone catalytic oxidation device, comprising a reactor, an ozone generator, a water collecting tank and a tail gas processor. In the present invention, a main stirrer and an auxiliary stirrer are arranged in the reaction chamber of the reactor, wherein the main stirrer is placed at the top of the reaction chamber, the auxiliary agitator is placed at the bottom end of the reaction chamber, and a microporous aerator is also arranged at the bottom of the reaction chamber, The microporous aerator evenly distributes the ozone in the reaction chamber, and realizes the full contact between the wastewater and ozone under the stirring of the main agitator and the auxiliary agitator. The contact effect of the catalyst, while destroying the ozone bubbles, increases the utilization rate of ozone, and strengthens the catalytic effect; in addition, the present invention is provided with a detachable packing plate on the stirring blade of the main stirrer, which can realize the catalyst and waste water during the stirring process. , ozone is fully contacted, and the convenient recovery of catalyst and the replacement of catalyst types can be realized; the invention also sets an exhaust port on the side wall of the reaction chamber, and the exhaust port is communicated with the water collection tank, and the excess ozone enters the water collection tank for processing. Reuse can further improve the utilization rate of ozone. The device provided by the invention solves the problems of low utilization rate of ozone, insufficient contact between catalyst and wastewater, and difficult recovery of catalyst in the prior art, and has the advantages of convenient operation and good wastewater treatment effect.

The present invention also provides a method for processing coal chemical concentrate by using the device described in the above scheme. In the invention, the ozone pre-oxidation reaction is firstly carried out under the condition that the filler plate is not filled with catalyst, the substances that can be oxidized by ozone alone in the wastewater are removed, and the usage amount of the catalyst is saved, and then the activated iron particle catalyst is filled in the filler plate, and the activated iron particle Under the action of the first stage ozone catalytic oxidation treatment, macromolecular pollutants in the wastewater are decomposed into small molecular pollutants, and then the carbon-based ozone oxidation catalyst is filled in the packing plate, and the second stage is carried out under the action of the carbon-based ozone oxidation catalyst. Ozone catalytic oxidation treatment uses carbon carrier to adsorb fine molecular pollutants while catalyzing ozone oxidation of pollutants. The method provided by the invention can reduce the amount of catalyst, save the use cost of the catalyst, improve the removal efficiency of pollutants, and achieve good sewage treatment effect.

Description of drawings

Fig. 1 is the structural representation of the ozone catalytic oxidation device of the present invention, wherein: 1-main agitator, 2-reactor exhaust port, 3-reactor water inlet, 4-reactor water outlet, 5-support layer, 6- Ozone gas storage layer, 7-main agitator stirring blade, 8-card slot, 9-packing plate, 10-packing plate with built-in holes, 11-microporous aerator, 12-auxiliary agitator, 13-ozone generator, 14- Ozone concentration detector, 15- Reactor cover, 16- Water collection tank, 17- Exhaust gas processor.

Detailed ways

The invention provides an ozone catalytic oxidation device, comprising a reactor, an ozone generator, a water collecting tank and a tail gas processor.

The ozone catalytic oxidation device provided by the present invention includes a reactor. In the present invention, the reactor includes a reactor body and a detachable reactor cover; the present invention has no special requirements on the shape of the reactor body, which can be a hollow cuboid or a hollow cylinder. The shape of the cover matches the reactor body, and it is sufficient that the reactor body can be sealed.

In the present invention, the inside of the reactor main body includes an ozone gas storage layer and a reaction chamber from bottom to top; the height of the ozone gas storage layer is preferably 4-10 cm; the bottom of the reaction chamber is provided with several microporous aerators The microporous aerator is communicated with the ozone gas storage layer. In a specific embodiment of the present invention, a pipeline is preferably used to communicate the microporous aerator and the ozone gas storage layer; the microporous aerator is connected to the ozone gas storage layer. The number of aerators is preferably 8 to 16, and the microporous aerators are preferably evenly arranged at the bottom of the reaction chamber.

In the present invention, a main stirrer and an auxiliary stirrer are further arranged in the reaction chamber, the main stirrer includes a main shaft and several stirring blades arranged on the main shaft, and the top of the main shaft is fixed on the reactor cover , in a specific embodiment of the present invention, it is preferable to set a block-shaped end at the top of the main shaft, and then set a support layer at the bottom of the reactor cover, and set the block-shaped end on the support layer, and the main shaft extends from the support layer. out, so that the main stirrer is fixed on the reactor cover. In the present invention, the number of stirring blades in the main stirrer is preferably 2 to 6, more preferably 4, each of the stirring blades is provided with two grooves, and the size of the two grooves is preferably Equivalently, a detachable packing plate is arranged in the card slot, and the catalyst can be filled in the packing plate. The invention can realize the convenient recovery of the catalyst and the replacement of the catalyst type by arranging the card slot and the packing plate.

In the present invention, the packing plate is preferably provided with several holes to further promote the sufficient contact between the waste water and the catalyst; the number of holes on a single packing plate is preferably 9, and the 9 holes are evenly arranged on the packing plate. In the present invention, one end of the stirring blade is fixed on the main shaft, and several stirring blades are staggered at 90° from top to bottom on the main shaft. In a specific embodiment of the present invention, the number of the stirring blades is preferably 4.

In the present invention, the length of the main shaft of the main stirrer is preferably 1/2 to 3/4 of the height of the reaction chamber; the stirring blade of the main stirrer is preferably in the shape of a cuboid, and the length of the stirring blade is 3/4～4/5 of the lateral dimension of the reaction chamber (when the reactor is a cylinder, the length of the stirring blade is 3/4 to 4/5 of the inner diameter of the reaction chamber, when the reactor is a cuboid, the stirring blade The length of the reaction chamber is 3/4 to 4/5 of the width of the reaction chamber), and the width of the stirring blade is preferably 1/6 to 1/5 of the height of the main stirrer.

In the present invention, the auxiliary stirrer is a spiral stirrer, comprising a main shaft and two stirring blades connected to the main shaft, and the main shaft is fixed at the bottom of the reaction chamber; the length of the main shaft of the auxiliary stirrer is preferably the length of the reaction chamber. 1/5 to 1/4 of the cavity height. The invention can strengthen the circulating flow of waste water by setting the auxiliary agitator, and can stir the ozone gas in the form of large bubbles at the same time, so as to improve the utilization rate of ozone.

In the present invention, the reactor cover is provided with an exhaust port, and the side wall of the reaction chamber is provided with a water inlet and a water outlet; the water inlet is preferably provided on the top of the side wall of the reaction chamber, and the water outlet is provided with at the bottom of the side wall of the reaction chamber.

The device provided by the invention includes an ozone generator; the gas outlet of the ozone generator is communicated with the ozone gas storage layer of the reactor through an ozone pipeline, and an ozone concentration detector is arranged on the ozone pipeline; There are no special requirements for the ozone generator and the ozone concentration detector, and those familiar to those skilled in the art can be used; the ozone generator is preferably an external oxygen tank.

The device provided by the present invention includes a water collecting tank. In the present invention, the water collection tank is preferably a closed water collection tank, the air inlet of the water collection tank is in communication with the exhaust port of the reactor, and the water outlet of the water collection tank is in communication with the water inlet of the reactor ; The water collecting tank is also provided with a water inlet, which is used to introduce the sewage to be treated into the water collecting tank. In the present invention, the water collecting tank is used to store the waste water to be treated, and the unused ozone in the reactor enters the water collecting tank through the exhaust port to realize the reuse of ozone and improve the utilization rate of ozone.

The device provided by the present invention includes an exhaust gas processor; the exhaust gas processor is communicated with the exhaust port of the water collecting tank, and is used for cleaning the unutilized ozone to avoid polluting the environment.

As a specific embodiment of the present invention, the structure of the ozone catalytic oxidation device is shown in Figure 1, in Figure 1: 1-main agitator, 2-reactor exhaust port, 3-reactor water inlet, 4- Reactor outlet, 5-support layer, 6-ozone gas storage layer, 7-main agitator stirring blade, 8-card slot, 9-packing plate, 10-packing plate built-in holes, 11-microporous aerator, 12-Auxiliary stirrer, 13-Ozone generator, 14-Ozone concentration detector, 15-Reactor cover, 16-Water collecting tank, 17-Exhaust gas processor.

The present invention also provides a method for utilizing the device described in the above scheme to process the concentrated liquid of coal chemical industry, comprising the following steps:

(1) Pass the coal chemical concentrate into the reaction chamber, install a packing plate without catalyst in the stirring blade of the main stirrer, and carry out ozone pre-oxidation treatment under the stirring conditions of the main stirrer and the auxiliary stirrer;

(2) replace the packing plate in the stirring blade of the main agitator with the packing plate filled with activated iron particles, and carry out the first-stage catalytic ozone oxidation treatment under the stirring conditions of the main agitator and the auxiliary agitator;

(3) replacing the packing plate in the stirring blade of the main agitator with a packing plate filled with a carbon-based ozone oxidation catalyst, and carrying out the second-stage catalytic ozone oxidation treatment under the stirring conditions of the main agitator and the auxiliary agitator;

In the treatment process of the steps (1) to (3), ozone is introduced into the reaction chamber by using an ozone generator.

In the present invention, the coal chemical industry concentrate is passed into the reaction chamber, a packing plate without catalyst is installed in the stirring blade of the main stirrer, and the ozone pre-oxidation treatment is carried out under the stirring condition of the main stirrer and the auxiliary stirrer. The present invention has no special requirements for the type of the coal chemical concentrate, and the coal chemical concentrate well-known to those skilled in the art can be treated by the method of the present invention, specifically such as biochemical secondary effluent, reverse osmosis concentrate effluent, etc.; In a specific embodiment of the invention, the COD value of the coal chemical concentrate is preferably 80-400 mg/L, and the UV ₂₅₄ is preferably 3-8.

Before the treatment, the present invention preferably adjusts the pH of the coal chemical concentrate to be treated to 8-9, more preferably 8.5 to 8.8; the pH-adjusting reagent is preferably sodium hydroxide; the present invention adjusts the pH of the coal chemical concentrate to The pH value is adjusted to 8-9, which is beneficial to the ozone catalytic oxidation reaction.

In the present invention, the stirring speed of the main stirrer is preferably 15-25 r/min, more preferably 18-22 r/min; the stirring speed of the auxiliary stirrer is preferably 100-150 r/min, more preferably 120 r/min ~130r/min.

In the present invention, the time of the ozone pre-oxidation treatment is preferably 10-20 min, more preferably 13-15 min; during the ozone pre-oxidation treatment process, the ozone generator is used to inject ozone into the reactor, and the ozone The feeding rate is preferably 0.7-1 g/min, more preferably 0.8-0.9 g/min; in the present invention, the catalyst is not filled in the packing plate first, and the substances that can be oxidized by ozone alone in the wastewater are removed by ozone pretreatment, thereby saving catalyst. dosage.

After the ozone pre-oxidation treatment is completed, the present invention replaces the packing plate in the stirring blade of the main agitator with a packing plate filled with activated iron shavings, and performs the first-stage catalytic ozone oxidation under the stirring conditions of the main agitator and the auxiliary agitator. deal with. In the present invention, the filling rate of activated iron shavings in the filler plate is preferably 30-60%; the preparation method of the activated iron shavings preferably includes the following steps: performing alkali washing and pickling on the iron shavings in sequence to obtain activated iron shavings; The alkaline washing agent for alkaline washing is preferably a sodium hydroxide solution, and the concentration of the sodium hydroxide solution is preferably 1-1.5 mol/L, more preferably 1.3-1.4 mol/L, and the time of the alkaline washing is preferably 1 to 1.5 mol/L. 22～24h, more preferably 21～23h; the pickling agent for pickling is preferably a hydrochloric acid solution; the concentration of the hydrochloric acid solution is preferably 0.1～0.5mol/L, more preferably 0.35～0.45mol/L; The pickling time is preferably 1-2h; the present invention has no special requirements for the source of the iron shavings, and iron shavings well-known to those skilled in the art can be used, and the present invention removes impurities on the surface of the iron shavings by alkali washing and pickling , the iron oxide is exposed to facilitate the contact reaction between the iron oxide and the waste water. After alkali washing and pickling, the surface of the iron shavings is completely silver-white, which is the activated iron shavings of the present invention.

In the present invention, the time of the first-stage catalytic ozone oxidation treatment is preferably 30-40 minutes, more preferably 33-35 minutes; during the first-stage catalytic ozone oxidation treatment, the stirring speed of the main stirrer, the auxiliary stirrer The stirring speed and the ozone introduction rate are consistent with the ozone pre-oxidation treatment process, and will not be repeated here. The invention decomposes macromolecular pollutants in wastewater into small molecular pollutants through the first-stage catalytic ozone oxidation treatment.

After the first-stage catalytic ozone oxidation treatment is completed, the present invention replaces the packing plate in the stirring blade of the main agitator with a packing plate filled with a carbon-based ozone oxidation catalyst, and conducts the first stage under the stirring conditions of the main agitator and the auxiliary agitator. Two-stage catalytic ozone oxidation treatment. In the present invention, the carbon-based ozone oxidation catalyst preferably includes a carrier and an active component supported on the carrier, the carrier is preferably activated carbon, and the active component is preferably manganese dioxide; According to the mass of 100%, the loading amount of manganese dioxide in the carbon-based ozone oxidation catalyst is preferably 3 to 5%, more preferably 4%; the present invention has no special requirements for the source of the carbon-based ozone oxidation catalyst. Commercially available products can be used or prepared by methods well known to those skilled in the art; the filling rate of the ozone oxidation catalyst in the packing plate is preferably 30-60%.

In the present invention, the time of the second-stage catalytic ozone oxidation treatment is preferably 30-40 minutes, more preferably 33-35 minutes; during the second-stage catalytic ozone oxidation treatment, the stirring speed of the main stirrer, the auxiliary stirrer The stirring speed and the ozone introduction rate are consistent with the ozone pre-oxidation treatment process, and will not be repeated here. In the second-stage catalytic ozone oxidation treatment process, the carbon-based ozone oxidation catalyst not only catalyzes the ozone oxidation reaction, but also adsorbs small molecular pollutants in the wastewater through the carbon carrier, thereby improving the removal efficiency of pollutants.

In the present invention, the cost of activated iron shavings is relatively low, while the cost of carbon-based ozone oxidation catalysts is relatively high. In the present invention, the activated iron shavings are used to carry out ozone catalytic oxidation reaction to remove most of the pollutants in the wastewater, and then carbon-based Ozone catalytic oxidation reaction is carried out on the base ozone oxidation catalyst to further improve the removal rate of pollutants; this method can reduce the use of high-cost catalysts and reduce the use cost of catalysts while ensuring the removal rate of pollutants.

The technical solutions of the present invention will be clearly and completely described below with reference to the embodiments of the present invention.

Example 1

The wastewater is taken from the effluent of the reverse osmosis concentrate of a coal-to-gas project. The main indicators of the wastewater are COD of 297.3 mg/L, pH of 7.7, and UV ₂₅₄ of 6.520.

The device in Figure 1 is used for wastewater treatment, wherein: the reaction chamber is cylindrical, the length of the main shaft of the main stirrer is 3/4 of the height of the reaction chamber, the length of the stirring blade is 3/4 of the radius of the reaction chamber, the height is 8 cm, and the width is The height of the main agitator is 1/6, and the number of stirring blades is 4; the length of the main shaft of the auxiliary agitator is 1/5 of the height of the reaction chamber; the number of microporous aerators is 16, and the number of holes on the packing plate is 9.

The processing steps are as follows:

The pH value of the coal gasification wastewater was adjusted to 9 with sodium hydroxide, and the packing plate without catalyst was firstly loaded into the main agitator blade, and the ozone pre-oxidation was carried out separately for 10 minutes. Then open the reactor cover, replace it with a packing board equipped with activated iron particles, catalytic oxidation treatment for 30min, and finally replace it with a carbon-based ozone oxidation catalyst (the carrier is activated carbon, the active component is manganese dioxide, and the active component is loaded 4%) of the packing plate, catalytic oxidation treatment for 30min, excess ozone into the water collection tank. Processing conditions: the stirring speed of the main stirrer is 20r/min, the stirring speed of the auxiliary stirrer is 120r/min, and the ozone feeding rate is 1g/min.

After the treatment of the above units, the effluent index is COD of 56.2mg/L and UV ₂₅₄ of 0.213, which can reach the water quality of the circulating cooling water system supplementary water specified in "Urban Wastewater Recycling and Utilization Industrial Water Quality" (GB/T19923-2005). standard.

The wastewater treatment efficiency of Example 1 is calculated, and the calculation formula is:

Treatment efficiency=[(influent COD-outlet COD)/influent COD]*100%;

It can be calculated that the wastewater treatment efficiency of Example 1 is 81.1%.

Test the amount of overflowed ozone by absorption-titration method, and calculate the utilization rate of ozone by the following formula:

Ozone utilization rate = (amount of ozone introduced - amount of overflowing ozone)/amount of ozone introduced × 100%.

The calculation shows that the utilization rate of ozone in this embodiment is 80%.

Example 2

The wastewater is taken from the biochemical secondary effluent of a coal-to-gas project. The main indicators of the wastewater are COD of 451.0 mg/L, pH of 7.4, and UV ₂₅₄ of 6.920.

The device in Fig. 1 is used for wastewater treatment, wherein: the reaction chamber is cylindrical, the length of the main shaft of the main stirrer is 3/4 of the height of the reaction chamber, the length of the stirring blade is 3/4 of the radius of the reaction chamber, the height is 10 cm, and the width is The height of the main agitator is 1/6, and the number of stirring blades is 4; the length of the main shaft of the auxiliary agitator is 1/5 of the height of the reaction chamber; the number of microporous aerators is 16, and the number of holes on the packing plate is 9.

The processing steps are as follows:

The pH value of the coal gasification wastewater was adjusted to 9 with sodium hydroxide, and a packing plate without catalyst was firstly loaded into the blade of the main agitator, and the ozone pre-oxidation was carried out separately for 20 minutes. Then open the reactor cover, replace it with a packing plate with activated iron particles, catalytic oxidation treatment for 40 minutes, and finally replace it with a packing plate with carbon-based ozone oxidation catalyst, catalytic oxidation treatment for 40 minutes, and excess ozone enters the water collection tank. Treatment conditions: the stirring speed of the main stirrer is 15r/min, the stirring speed of the auxiliary stirrer is 125r/min, and the ozone feeding rate is 1g/min.

After the treatment of the above units, the effluent index is COD of 47.2mg/L and UV ₂₅₄ of 0.204, which can reach the water quality of the circulating cooling water system supplementary water specified in "Urban Wastewater Recycling and Utilization Industrial Water Quality" (GB/T19923-2005). standard.

The wastewater treatment efficiency was calculated according to the method in Example 1, and it was obtained by calculation that the wastewater treatment efficiency of Example 2 was 89.5%.

According to the method in Example 1, the utilization rate of ozone was calculated, and the calculation showed that the utilization rate of ozone in this example was 75%.

Comparative Example 1

The waste water used is the same as in Example 1, other conditions are the same as in Example 1, and only the treatment steps are changed to: adjust the pH value of the coal gasification waste water to 9 with sodium hydroxide, and install the activated iron shavings in the main stirrer blade. The packing plate is subjected to ozone catalytic oxidation treatment, and the time of catalytic oxidation treatment is 80 minutes. The COD value of the effluent is 94.9 mg/L, and the UV ₂₅₄ value is 0.901.

The wastewater treatment efficiency was calculated according to the method in Example 1. After calculation, the wastewater treatment efficiency of Comparative Example 1 was 68%. Compared with Example 1 and Comparative Example 1, the wastewater treatment efficiency is improved by 13%.

According to the method in Example 1, the ozone utilization rate is calculated. It can be seen from the calculation that the ozone utilization rate in Comparative Example 1 is 60%. Compared with Comparative Example 1, the ozone utilization rate in Example 1 is increased by 20%.

Comparative Example 2

Other conditions are the same as in Implementation 2, except that the treatment steps are changed to: adjust the pH value of the coal gasification wastewater to 9 with sodium hydroxide, and install a packing plate equipped with a carbon-based ozone oxidation catalyst in the main stirrer blade for ozone catalytic oxidation treatment, The time of catalytic oxidation treatment was 80 min. The effluent COD value was 184.9 mg/L, and the UV ₂₅₄ value was 2.321.

The wastewater treatment efficiency of Comparative Example 2 was calculated according to the method in Example 1, and the results showed that the wastewater treatment efficiency of Comparative Example 2 was 59%. Compared with Example 2 and Comparative Example 2, the wastewater treatment efficiency is improved by 16%.

The ozone utilization rate of Comparative Example 2 was calculated according to the method in Example 1. The calculation showed that the ozone utilization rate in this example was 50%. Compared with Comparative Example 2, the ozone utilization rate of Example 2 was increased by 25%.

It can be seen from the above embodiments that the ozone catalytic oxidation device of the present invention can effectively improve the utilization rate of ozone, save the usage of ozone and catalyst, reduce the damage rate of the catalyst, thereby save the catalyst, and ensure that the COD concentration of the effluent meets the emission standard , which can meet the actual operation needs.

The above are only the preferred embodiments of the present invention. It should be pointed out that for those skilled in the art, without departing from the principles of the present invention, several improvements and modifications can be made. It should be regarded as the protection scope of the present invention.

Claims (9)

1. a method for processing coal chemical concentrate, is characterized in that, the ozone catalytic oxidation device adopted comprises reactor, ozone generator, water collecting tank and tail gas processor; The reactor includes a reactor main body and a detachable reactor cover; the inside of the reactor main body includes an ozone gas storage layer and a reaction chamber from bottom to top; a number of microporous aerators are arranged at the bottom of the reaction chamber, the microporous aerator communicates with the ozone gas storage layer; The reaction chamber is also provided with a main stirrer and an auxiliary stirrer, the main stirrer includes a main shaft and several stirring blades arranged on the main shaft, and the top of the main shaft is fixed on the reactor cover; Two clamping slots are arranged on the stirring blade, and a detachable packing plate is arranged in the clamping slot; one end of the stirring blade is fixed on the main shaft, and several stirring blades are installed on the main shaft in a 90° staggered manner from top to bottom; The auxiliary stirrer is a spiral stirrer, comprising a main shaft and two stirring blades connected to the main shaft, and the main shaft is fixed at the bottom of the reaction chamber; An exhaust port is provided on the reactor cover, and a water inlet and a water outlet are provided on the side wall of the reaction chamber; The gas outlet of the ozone generator is communicated with the ozone gas storage layer of the reactor through an ozone pipeline, and an ozone concentration detector is arranged on the ozone pipeline; The air inlet of the water collection tank is communicated with the exhaust port of the reactor; the water outlet of the water collection tank is communicated with the water inlet of the reactor; The exhaust gas processor is communicated with the exhaust port of the water collecting tank; The processing method is: (1) pass the coal chemical concentrate into the reaction chamber, install a packing plate without catalyst in the stirring blade of the main stirrer, and carry out ozone pre-oxidation treatment under the stirring conditions of the main stirrer and the auxiliary stirrer; (2) replace the packing plate in the stirring blade of the main agitator with the packing plate filled with activated iron particles, and carry out the first-stage catalytic ozone oxidation treatment under the stirring conditions of the main agitator and the auxiliary agitator; (3) replacing the packing plate in the stirring blade of the main agitator with a packing plate filled with a carbon-based ozone oxidation catalyst, and carrying out the second-stage catalytic ozone oxidation treatment under the stirring conditions of the main agitator and the auxiliary agitator; In the treatment process of the steps (1) to (3), ozone is introduced into the reaction chamber by using an ozone generator. 2 . The method for processing coal chemical concentrate according to claim 1 , wherein the number of stirring blades in the main agitator is 2-6; the packing plate is provided with several holes. 3 . 3 . The method for processing concentrated liquid of coal chemical industry according to claim 1 , wherein the number of the microporous aerators is 8 to 16, and the microporous aerators are evenly arranged at the bottom of the reaction chamber. 4 . cloth. 4 . The method for processing coal chemical concentrate according to claim 1 , wherein the length of the main shaft of the main stirrer is 1/2 to 3/4 of the height of the reaction chamber; The length of the main shaft is 1/5-1/4 of the height of the reaction chamber. 5 . The method for processing coal chemical concentrate according to claim 1 , wherein the stirring blade of the main stirrer is in the shape of a cuboid, and the length of the stirring blade is 3/4 to 4 of the lateral dimension of the reaction chamber. 6 . /5, and the width is 1/6 to 1/5 of the height of the main stirrer. 6. The method for processing coal chemical concentrate according to claim 1, wherein in the steps (1) to (3), the stirring speed of the main agitator is 15 to 25 r/min, and the The stirring speed is 100～150r/min. 7. The method for processing coal chemical concentrate according to claim 1, wherein the time for the ozone pre-oxidation treatment is 10-20 min, and the time for the first-stage catalytic ozone oxidation treatment is 30-40 min, The time for the second-stage catalytic ozone oxidation treatment is 30-40 minutes. 8 . The method for processing coal chemical concentrate according to claim 1 , wherein the introduction rate of the ozone is 0.7-1 g/min. 9 . 9 . The method of claim 1 , wherein the carbon-based ozone oxidation catalyst comprises a carrier and an active component supported on the carrier, the carrier is activated carbon, and the active component It is divided into manganese dioxide; based on the mass of the carbon-based ozone oxidation catalyst as 100%, the loading amount of manganese dioxide in the carbon-based ozone oxidation catalyst is 3-5%.

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